Water-soluble salts of derivatives of 4:4&#39;-diaminostilbene-2:2&#39;-disulfonic acid for enhancing the brightness of organic fibrous material



United States Patent p WATER-SOLUBLE SALTS OF DERIVATIVES OF 4:4'-DIAMINOSTILBENE-2:2'-DISULFONIC ACID FOR ENHANCING THE BRIGHTNESS OF OR- GANIC FIBROUS MATERIAL Franz Ackermann, Binningen, Switzerland, assignor to Ciba Limited, Basel, Switzerland No Drawing. Application October 2, 1950 Serial No. 188,071

Claims priority, application Switzerland October 14, 1949 15 Claims. (Cl..252-89) This invention provides new derivatives of 4:4"-diaminostilbene-Z:2'-disulfonic acid of the general formula o 0 Jr i in which W represents an organic radical bound" to the carbon atomof the triazine ring by an --O- or -S- bridge, which radical may contain substituents, and X, Y and Z each represent -NH the radical of a primary or secondary amine bonded by the nitrogen atom to the triazine rin'g, chlorine, bromine, or a radical of the kind represented by-W, and in which derivatives not more than one of the radicals Y and Z represents chlorine or bromine, or salts of such derivatives.

The invention also includes a process for themanufacture of derivatives of the above general formula or salts thereof, wherein 2 molecular proportions of cyanuric chloride or cyanuric bromide are reacted in any order of succession with (a) 1 molecular proportion of 4:4'-diaminostilbene-2:2'-disulfonic acid or a salt thereof, (b) 1-4 molecular proportions of an aliphatic,

aromatic, araliphatic, hydroaromatic of heterocyclic hydroxyor mercapto-compound or an alkali compound of such hydroxy or mercapto compound and (c) with 0-3 molecular proportions of ammonia of l-3 molecular proportions of a primary or secondary amine, and wherein .a total of 2-4 molecular proportions of compounds specified under (b) and (c) are reacted and the synthesis is socarried out that in theresulting product Y and Z do not both represent chlorine or bromine.

The same compounds can also be prepared by starting from a 4-aminostilbene-2z2l-disulfonic acid which contains in the 4'-position a group convertible into an amino group, such as an acylamino or nitro group.

If 4-nitro-4'-aminostilbene-2:2-disulfonic acid is used as starting material 1 molecular proportion of cyanuric chloride of cyanuric bromine is reacted with l molecular proportion ofthe aforesaid acid or a water-soluble salts thereof and with a total of 1-2 molecular proportions of compounds specified under (b) and c), the nitro group in the resulting condensation product is converted by reduction into an amino group, and a molecular proportions required by the above described constitution of the final product. i 1

The new compounds of the foregoing formula and also their salts are not dyestuffs in character, but owing to their constitution they possess a more or less pronounced afiinity for a very wide variety of substrata, such as vegetable and animal fibers. On these substrate. they exhibit in ultraviolet light a blue to violet fluorescence. By virtue of this property the products of the invention are capable of improving the white appearance of undyed materials and the purity of color of dyed materials. i

Among the hydroxyand mercapto-compounds to be used as starting materials there may be used in the aliphatic series saturated, unsaturated, straight or branched chain alcohols and mercaptans containing, for example, 1-10 carbon atoms, which may contain in addition to a hydroxyl or mercapto group further substituents such as halogen atoms, carboxyl or sulfonic acid groups orpolyalkylene-glycol radicals. Especially suitable, however, are the members of this series of lower molecular weightcontaining 1-6 carbon atoms such, for example, as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, alkyl alcohol, butyl alcohol, secondarybutyl alcohol, tertiary-butyl alcohol, hexyl alcohol, 2- ethyl-butanol, hydroxyethane sulfonic acid, allyl mercaptan, amyl mercaptan, thio-glycollic acid or thioethylene glycol. The aromatic members of these classes of compounds may be derived from any desired aromatic compounds, but above all from benzene or naphthalene. In addition to an HO- or HS-group they may contain, if desired, further substituents such as halogen atoms, alkyl groups, etherified hydroxyl groups, acylated or dialkylated amino groups, or carboxylic acid or sulfonic acid groups. There may be mentioned phenol, orthoor metaor para-chlorophenol, 2:4-di- As primary or secondary amines for use in the present invention there may be used aliphatic, aromatic, araliphatic or heterocyclic amines. As aliphatic amines there are used advantageously alkylamines, dialkylamines, hydroxyalkylamines, bis (hydroxyalkyl) amines and N:N'-dialkyl-alkylene diamines. Either straight chain or branched chain, saturated or unsaturated members of these classes of compounds containing, for example, 1-18 carbon atoms may be used. Especially suitable are those containing 1-4 carbon atoms in the carbon chain. There may be mentioned for example, methylamine, ethylamine, propylamine, isoprop'ylamine, butylamine, isobutylamine, allylarnine, mono-ethanolamine, di-isobutylamine and N':N-dimethylethylene diamine. However, there may also be used aliphatic amines substituted in the alkyl radical such, for example, as taurine.

The aromatic amines may be monoor polynuclear and may if desired contain. further substituents. Advantageously aniline or. a nuclear substitution product thereof is used such, for example, as orthoor paratoluidine, various chloranilines, orthoor para-anisidine and thelike. However, naphthylamines, such as aor fi naphthylamine or nuclear substitution products of these compounds may be used in the present invention.

' -lieterocyclic amines which can be used in the present or ar-tetrahydroi -naphthyl invention may contain 1 or more heterogen atoms. There may be mentioned piperidine, a-pipecoline, morpholine, pyrrolidine, imidazoline, benzimidazole, 2- aminothiazole, S-aminotetrazole and tetrahydroquinoline.

As salts of products used in the invention there may be used above all water-soluble salts with ammonia or amines, but advantageously the alkali metal salts.

The new derivatives of 4:4'-diaminostilbene-2:2'-disulfonic acid of the present invention may be made, for example, by reacting 2 molecular proportions of cyanuric chloride by a method generally known for reacting it with amines, for example in the presence of water or a mixture of water with an organic solvent, such as acetone, and if the desired in the presence of buffers or acid-binding agents, such as sodium acetate, alkali carbonates or alkali hydroxides with 1 molecular proportion of 4:4- diaminostilbene-2:2'-disulfonic acid or a salt thereof, and then reacting the resulting 4:4-bis-[2z4-dichloro-1:325- triazyl-(6)-amino]-stilbene-2:2-disulfonic acid or a salt thereof, if desired in the presence of a butter or acidbinding agent, such as sodium acetate or an alkali carbonate or alkali hydroxide, with 2 or 4 molecular proportions of a hydroxy or mercapto compound of the kind described above or an alkali compound thereof. It is also possible'first to react 4:4-bis-[2z4-dichloro-1:3z5- tn'azyl-(6)-amino]-stilbene-2:2disulfonic acid with 2 molecular proportions of a hydroxy or mercapto compound and then with 2 molecular proportions of ammonia or 2 molecular proportions of 1 of the aforesaid amines.

In this manner symmetrical products are obtained.

If it is desired to produce asymmetrically substituted compounds there is advantageously used .as starting material a 4-nitro-4'-aminostilbene-2:2'-disulfonic acid. The latter compound is condensed by a method in itself known with cyanuric chloride to form 4-nitro-4'-[2:4- dichloro- 1:325 triazyl-(6)-amino]-sti1bene-2:2'-disulfonic acid, and then at least one of the two chlorine atoms is exchanged by reaction with a compound mentioned under (b) and above.

(c), at least 1 molecular proportion of a compound mentioned under (b) entering into reaction.

It is also possible to react cyanuric chloride in any order of succession depending on the constitution of the final product first with the compounds under (b) and (c) and then with 4:4'-diaminostilbene-2:2'-disulfonic acid.

The two last mentioned methods generally lead to mixtures of diiferent products, which however, possess substantially the same properties, as the pure compounds.

In the reactions illustrated above cyanuric bromide may be used instead of cyanuric chloride.

Among the compounds obtainable by the invention the following may be especially mentioned:

A. Compounds having combinations of substituents falling within the general formula in which R represents an aliphatic, aromatic, araliphatic, hydroaromatic or heterocyclic radical, which may contain substituents, .X and Y represent NH or the radical of a primary or secondary amine which is bound to the triazine ring by means of the nitrogen atom.

Compounds of this kind are for example 4:4-bis-[2- (ortho-chlorophenoxy) 4 hydroxyethylamino-l :3 :5-triazyl-(6)-amino]-sti1bene-2:2-disulfonic acid, 4:4 bis-[2- methoxy-4-bis-(B-hydroxyethyD-amino 1:325 triazyl-(6)- amino]-stilbene-2:2=disulfonic acid, 4:4 -bis-[2-benzyloxy-4-methylamino 12 3:5 triazyl (6) amino]-stilbene- 2:2-disulfonic acid, 4:4 bis [2-cyclohexyloxy-4-(fl-hydroxyethylamino) 1:3:5 triazyl-(6)-amino]-stilbene-2:2- disulfonic acid, 4:4 bis [2-para-methoxyphenoxy-4-(flhydroxyethylamino) 1:3:5-triazyl (6) aminol-stilbene- 2:2'-disulfonic acid, and also 4:4-bis-[2-phenoxy-4-morpholino-l:3:5-triazyl-(6)-aminol-stilbene 2:2 disulfonic Alternatively, 1 or 2 chlorine atoms of the cyanuric acid of the formula /C Biz-05: /N\ /N\ /CH2-C{I\n o N-C J-NH oH=oH- 1vn 3 (|J-N\ 0 GHQ-C I11 N h l N CHPCH:

\ 0111 son:

chloride may first be exchanged by reaction with 1-2 mols of a compound mentioned under (b) or (c) and the condensation with 4-nitro-4-aminostilbcue-2:Z' disulfonic acid carried out thereafter.

The nitro group in the condensation product so obtained is converted into an amino group by reduction, for example, with iron in the presence of an acid, and the amino group may be substituted in a manner analogous to that described above in connection with the other amino group, a total of at least one molecular proportion of a compound mentioned under (b) being brought into reaction.

The production of asymmetrical products can also be carried out by starting from 4:4'-diaminostilbene-2:2'-disulfonic acid, by first reacting the latter with 2 molecular proportions of cyanuric chloride, and reacting the condensati-on product so obtained with a total of 2-4 molecular proportions of compounds mentioned under (b) and or salts of the foregoing compounds.

B. Compounds of the general formula in which R represents an aliphatic, aromatic, araliphatic, hydroaromatic or heterocyclic radical, which may contain substituents, X and Y represent NH or the radical of a primary or secondary amine, for example, 4-[2- phenoxy 4 (B-hydroxyethyD-amino 123:5 triazyl-(6) amino]-4'-[2-chloro-4-bis-(,8-hydroxyethyl) amino-1:35- triazyl-(6)-amino]-stilbene 2:2 disulfonic acid of the formula C. Compounds of the general formula amino-l:3:5-triazyl-(6)-aminol 4 [2-methylamino-4-phydroxyethylamino 123:5 triazyl (6) aminolstilbene 2:2-disulfonic acid of the formula or 4-[2-(ortho-methyl-phenoxy)-4-bis-(fl-hydroxyethyl) amino-1:3:5-triazyl (6) amino] 4' [2:4-diamino-lz3z5- triazyl-(6)-amino]-stilbene-2:2-disulfonic acid; 4-[2-phenoxy-4-p-hydroxyethylamino-1:3:5-triazyl-(6)-amino] 4-- [Z-ethylamino-4-ortho-anisidino-l :3 5 -triazyl 6 -amino] stilbene-2:2-disulfonic acid, or 4-[2-(parasulfophenoxy)- 4-ethylamino-lr3z5-triazyl (6) amino] 4-[2:4-di-(ortl1och1oranilino)-1:3z5-triazyl (6) amino]-stilbene2:2-disu1- fonic acid or 4-[2-phenoxy-4-methylamino-1:3:5-triazyl- (6)-aminol-4' [Z-anilino 4 methylamino-l23:5-triazyl- (6)-amino]-2:2-disulfonic acid.

D. Compounds of the general formula N N g i g a N N 03H 03H a c t E i-a l S-R in which R represents an aliphatic, aromatic, araliphatic,

N N r W N N N N SOzH sous \O/ SIR 1 in which R represents an aliphatic, aromatic, araliphatic, hydroaromatic or heterocyclic radical, and X and Y each represent --NH or the radical of'a primary or secondary amine which is bound by the nitrogen atom to the triazine ring.

i Compounds of the general formula SOQH in in which R has the meaning given under D and X, Y and Z each represent -NH or the radical of a primary or secondary amine bound by the nitrogen atom to the triazine ring.

G. Compounds of the general formula QsH 053: (5R -R in which R has the meaning given under C, and X and Y represent NH or the radical of a primary or secondary amine bound by the nitrogen atom to the triazine ring.

The compounds of this invention can be used by impregnating the material to be improved with solutions, especially aqueous solutions, of the compounds in question and drying the material, after centrifuging or squeezing it. For example, white goods, especially after an ordinary washing operation, may be after-treated with the compounds of the invention. Moreover, the new products can be used for after-treating printed cellulose materials. I i

The compounds of the invention may also be applied to materials for improving them in the course of manufacture, for example, by adding them to a paper pulp.

Small quantities of the compounds of the presentinvention generally sufiice to produce an improvement, that is to say to improve the whiteness of undyed fibrous materials or the purity of color of dyed fibrous materials.

The compounds of the invention may also be used in admixture with auxiliary substances such as are used for improving fibrous materials, for example, in conjunction with washing agents, for example, with soaps, salts of sultonated washing agents, for example, salts of sulfonated benzimidazoles substituted at the 2-carbon atom by an alkyl radical of high molecular weight, and salts of monocarboxylic acid esters of 4-sulfophthalic acid with fatty alcohols of high molecular weight, or in conjunction with fatty alcohol sulfonates or condensation products of higher fatty acids with aliphatic hydroxyor aminosulfonic acids. In this manner the material to be improved can be simultaneously washed and bleached. An especially pronounced brightening effect is obtained by treating undyed vegetable or animal fibers, especially cotton or Wool, with such mixtures containing washing agents.

As materials which can be improved in accordance with the invention, there may be mentioned the followmg:

Nitrogenous natural or artificial materials such as wool, silk or synthetic polyamide fibers; also cellulose materials such as cellulose, paper, and textile materials of cotton, linen, regenerated cellulose including staple fibers of regenerated cellulose; and finally synthetic materials, for 2:2'-disulfonic acid or of 4:4'-bis-[2-(para-rnethoxyexample, those produced by polymerization. The best phenoxy)-4-(fl-hydroxyethylamino) 1:315 -triazyl- (6)- effects are obtained, however, on vegetable and animal amino]-stilbene-2:2-disulfonic acid in the form of a pale fibers. The material to be improved may be in any powder which exhibits very similar properties. desired form, for example, in the form of fibers or films. 5 Furthermore, the material may be, for example, undyed, Example 2 dyed or printed.

The following examples illustrate the invention, the -5 Parts of cyamll'ic chloride are condensed wi h 18.5

parts being by weight unless otherwise stated and the parts Of 4:4'-diaminostilbene-2:2-d.isulfonic acid and 9.5

"relationship of parts by weight to parts by volume being 10 Parts of P1161101 in the manner described in Example the same a that of th kilogram t th lit there are added, to the reaction mixture heated at 40-45 C., 27 parts of an aqueous monoethylamine solution of p 50 percent strength, the temperature is raised to 60 C.

A solution, neutralized with sodium carbonate of 18.5 and the whole is stirred for about 24 hours at 60 C. parts ofg 4:4-diaminostilbene-2:2'-disulfonic acid is added 18 The whole is then allowed to cool, the resulting condensain the course of about 10 minutes at -5 C. to 18.5 parts tion product is separated by the addition ofsodium chloof cyanuric chloride suspended in finely divided form in r and the Product is Separated y filtration, s d a mixture consisting of 50 parts of acetone, 100 parts of with sodium chloride solution and dried. The resulting water and 100 parts of ice. Then, a solution of 5.5 parts disodium salt of 4:4-bis-[2-phenoxy-4-ethylamino-l:3:5- of sodium carbonate in 50 parts of water are introduced triaZy1-(6)-aminolstilbene-2:2'-disulfonic acid of the Example 1 dropwise in the course of 1 hour so that the reaction formula /N /N ont-on Nn-p o-nN--on=c11 NHC| -NnoH2-on1 It N A N N H Om:

mixture has a weakly acid to neutral reaction throughout, is a slightly yellowish powder whose aqueous solutions the temperature being allowed to rise slowly to C. exhibit a violet-blue fluorescence in ultraviolet light. To the neutral reaction mixture so obtained containing 30 By using instead of 27 parts of a monoethanolamine no more starting material are added 9.5 parts of phenol, solution of 50 percent strength, an equivalent quantity the temperature is raised to -45 C. and the whole is of dlmethylamine, N':N-diethylethylene diamine or stirred for 3 hours at that temperature while adding 100 morpholine, the following compounds are obtained in the parts of a normal solution of caustic soda so that the form of yellowish powders having similar properties: reaction mass has a neutral to weakly alkaline reaction 40 the disodium salt 0f4:4-bis-[2-phenoxy-4-dimethylaminothroughout. To the neutral mixture, 7 parts of mono- 1 3:5 -triazyl-(6)-amino] -stilbene-2:2-disulfonic acid; the ethanolamine are added, the temperature is raised to 75 dlSOdIIIm Salt 9 -P Y- P n0-1335- C. in the course of 2-3 hours and stirring is continued tr1a y )-am1no]-stilbene-2:2-disulfonic acid, the disodifor 5 hours at that temperature, while the hydrochloric um salt of 4:4'-bis-[2-phenoxy-4-(N:N-diethyl-ethylacid formed is neutralized by the gradual addition of a n6 i Y 0- tilb nc-2:2' disulsolution of 5.3 parts of sodium carbonate in parts of f IiC a id.

water. The whole is then allowed to cool, whereupon part of the resulting condensation product precipitates in the form of a solid powder. By adding sodium chloride the remainder of the condensation product is precipitated.

Example 3 2.4 parts of metallic sodium are dissolved at about C. in 100 parts of 2-ch1orophenol, 6 parts of the di- The whole is filtered, the residue is washed with sodium sodium salt of 4:4'-bis-[2-chloro-4-methylamino-1:3:5- chloride solution and the resulting disodium salt of 4:4'- triazyl-(6)-amino]-stilbene-2:2-disulfonic acid are then bis [2-phenoxy-4-(p-hydroxyethylamino) 123:5 triazyladded and the whole is stirred for 3-4 hours at a tem- (6)-amino]-stilbene-2:2-disulfonic acid of the formula perature of 80 C. The resulting reaction mixture is then I i nooniom-un-p C-HNOOH=CH- -NHCII o-Nn-onioni-on it it E! N it 0311 S0311 is dried. It is a pale yellow powder, which is soluble in introduced at 0-l0 C. into a sodium hydroxide solution, water. Wool which has been treated with an aqueous and the condensation product so obtained is precipitated solution of this product in the presence of an acid, for by the addition of sodium chloride, the product is sepaexample, acetic acid, has a whiter appearance than wool rated by filtration and washed with an aqueous solution which has been treated without this addition. of sodium chloride until neutral and free from chloro- By using instead of 9.5 parts of phenol an equimolecuphenol. After drying the disodium salt of 4:4-bis-[2- lar quantity of 2-chlorophenol or 4-methoxyphenol in (ortho-chlorophenoxy)-4-methylamino-l:3:5-triazyl-(6)- the reaction described above, there is obtained the diamino]-stilbene-2:2'-disulfonic acid is obtained in the sodium salt of 4:4-bis-[2-(ortho-chlorophenoxy)-4-(pform of a pale powder, aqueous solutions of which are hydroxyethylamino)-lz3t5-triazyl-(6) amino] stilbenej suitable for brightening vegetable or animal materials.

2,846,397 9 r v 10 r Example4 course of 10 minutes to the above suspension at +5 C.

, Then, a solution of 5.5 parts of sodium carbonate in 50 ffi gi i g gf parts of Water is added dr-opwise to the resulting reaction fonic acid of the formula mixture in the course of 1 hour in such manner that the N HZN- OH=CH- Nit-4|: ?NH-CH2CH2OH A A N Ii 03H 03H \C/ l IHCHs are stirred with 50 parts of water and neutralized with 15 mixture has a neutral to weakly acid reaction throughout.

sodium carbonate. The resulting solution is added in the 8 parts of an aqueous mono-methylamine solution of 40 course of 5 minutes to an aqueous suspension of 2 parts percent strength are then added, the temperature is raised of finely divided cyanuric chloride at l-5 C., and the in the course of 1 hour to 35 C., and the whole is stirred reaction mass is then neutralized at l-10 C. by means at that temperature for 3 hours. The hydrochloric acid of a solution of 0.5 part of sodium carbonate in 5 parts 90 formed in neutralized by the gradual addition of a soluof water. As soon as the starting material can no longer H tion of 5.5 parts of sodium carbonate in 50 parts of be detected, 1.1 parts of ortho-cresol are added, the temwater. Finally, parts of mono-ethanolamine are added perature is allowed to rise 'to 4045 C., and 10 parts of to the reaction mixture, the temperature is raised to 70 a normal solution of caustic soda are gradually added C., and the whole is stirred at this temperature for 6 dropwisein the course of 3 hours so that the reaction hours. The condensation product so formed is precipimass is maintained neutral to very slightly alkaline rated by the addition of sodium chloride, and separated by throughout. 1.1 parts of diethanolamine are then added filtration, washed neutral with sodium chloride solution to the neutral mixture, the temperature is raised to 70-.75 and then reduced. For the latter purpose the product is C., and the whole is stirred for 6 hours at that tempera-' introduced at 90-l00 C. in the course of 1 hour into a ture, while the hydrochloric acid formed is neutralized mixture of 15 parts of glacial acetic acid, 66 parts of iron by the gradual addition of 0.5 part of sodium carbonate filings and 500 parts ofWater. As soon as the nitro in 5 parts of Water. The whole is then allowed to cool, body has disappeared the reaction mixture is rendered sodium chloride is added, the precipitated condensation alkaline with sodium carbonate at -60 C., filtered, and product is separated by filtration, washed with aqueous the resulting 4-amino-4-i2-methylarnino-4- (13-hydroxysodium chloride solution and dried. The disodium salt 35 ethylarninm-l:3:5-triazyl-(6)-amino]-stilbene-2:2'-disulof 4-[2-(ortho-methylphenoxy)-4-bis-(,B hydroxyethyl)- fonic acid is precipitated from-the filtrate by the addition amino-1:3:5-triazy1-(6)-amino]-4-[2-methyl amino 4- of dilute hydrochloric acid, the product is separated by (/3-hydroxyethylamino)-1:3z5-triazyl- (6) amino] -stilfiltration, washed free from mineral acid by means of bene-2:2'-disulfonic acid of the formula Water and dried.

HOCHrCHz N\ /N\ NC CHNCH=CH-NH(|1 CNH-CHCH1OH HOCHrC: ii l t 1 A N 03H sour o 0 (L9 IL'ECH;

is obtained in the form of a pale powder, which dissolves Example 5 in water to give a bluish fluorescence in ultraviolet light.

By using as starting material, instead of 5.4 parts of 4-amino-4'-[2-methylamino 4 18 hydroxyethylaminol 1:3:5-triazyl-(6)-amino]-stilbene-2:2-disulfonic acid, an equivalent quantity of 4-amino-4-[2:4-diamino-1:3z5- triazyl-'(6)-amino] -stilbene-2:2'-disulfonic acid there is obtained a product having similar properties.

A mixture of products having properties similar to those of the abovedescribed compound is obtained by condensing 1 molecular proportion of 4:4'-diaminostilbene-2:2'-disulfonic acid with 2 moleoularproportions of cyanuric chloride, condensing the condensation product with 1 molecular proportion of ortho-cresol and finally reacting the product with 1 molecular proportion each of diethanolamine, ethanolamine and methylamine.

The -4-amino 4'-[2-rnethylamino-4 (18 hydroxyethylamino) -1 :3 :*5-rtriazy-l- ('6 4aminol -sti-1bene 2 Zdisulfonic acid used as starting material may be prepared as follows:

A solution of 20 parts of cyanuric chloride in 100 parts disulfonic acid is added at 0-5 C. in the course of about lOminutes to 18.5 parts of cyanuric chloride, which are suspended in a finely divided form in a mixture consisting of 50 parts of acetone, 100 parts of water and 100 parts of ice. A solution of 5.5 parts of sodium carbonate in 50 parts of water is then introduced dropwise in the course of 1 hour in such manner that the reaction mixture ismaintained weakly acid to neutral throughout, the temperature being allowed to rise slowly to 10 C. at the same time. To the neutral reaction mixture obtained in this manner and containing no starting material 7.8 parts of thioethylene glycol are added at 8-10 C. and then a solution of 4 parts of sodium hydroxide in 100 parts of water is added in the course of 1 hour, so that the reaction mixture is maintained neutral to weakly alkaline throughout, While the temperature is allowed to rise to 20-25 C. 11 parts of diethanolamine are then added, the temperature is raised in the course of 1-2l1ours to 70 C., and the 0f acetone is Poured info 100 Parts of ice whole is stirred for 6 hours at that temperature while and 100 parts of Water, and a solut on of 47.6 parts of 4- neutralizing the hydrochloric acid formed with 5.3 parts nitr0-4'-8min0Stil 1 m acld p t of sodium carbonate in 50 parts of water. After cooling strength) in 400 parts of water and neutralized with S0- the resulting condensation product is precipitated by the idium hydroxide is added dropwise, while stirring, in the addition of sodium chloride, :andthe product is separated A solution of 18.5 parts of 4:4-diaminostilbene-2:2'-

2,846,397 11 12 by filtration and dried. The resulting disodium salt of there are obtained products having similar properties, for 4:4'-bis-[Z-(fi-hydroxyethylthio)-4-bis-(p hydroxyethyl)- example the disodium salt of 4:4-bis-[2(2:S-dimethylamino-l:3z-5-triazyl-(6)-amino]-stilbene 2:2'-disulfonic phenylthio) 4-morpholino-l:3:5-triazyl-(6)-amino]-stilacid of theformula bene-2:2'-disulfonic acid, the disodium salt of 4:4-bis-[2- HOCHZCE: N\ /N\ /CH2GH2OH 03H soar: C r

nocHicHi s S-CHzCHrOH is a pale yellow powder soluble in water, which When (Z-mercapto-thiazolino)-4-(fl-hydroxyethylamino)-1:3:5- applied to cellulose material from solution exhibits in triazyl-(d)-amino]-stilbene-2:2'-disulfonic acid or the diultraviolet light a blui h fluorescence, 15 sodium salt of 4:4-bis-[2(2-mercapto-thiazolino)-4-m0rpholino-l :3 5 -triazyl-(6)-amino] -stilbene-2:2 disulfonic Example 6 acid A solution, neutralized with sodium carbonate, of 18.5 Example 7 parts of 4:4'-diarninostilbene-2:2'-disulfonic acid is added r in the course of about 10 minutes at 0.5 C. to 18.5 parts Parts 0- :[Z-BthYIammO- l-(Ortho-amof cyanuric chloride suspended in finely divided form in S1d m)'1:3=5'maZY1'(6)'amm]St11bene'2i2 dlsulfomc a mixture consisting of 50 parts of acetone, 100 parts of amid the formula water and 100 parts of ice. A solution of 5.5 parts of N sodium carbonate in 50 .parts of water is then added dropwise in the course of 1 hour so that the reaction 5 EN OH'GH mixture is maintained weakly acid to neutral throughout, g H CH the temperature being allowed to rise slowly to 10 C. a 3 at the same time. To the neutral reaction mixture so ob- I NHCHzoHa tained and containing no more starting material, are added 11 parts of thiophenol, the temperature is raised to are condensed in the manner described in Example 4 40 C. and the whole is stirred for 4 hours at this temwith 1.9 parts of cyanuric chloride. As soon as the perature, while 100 parts of a normal solution of caustic starting material can no longer be detected 0.95 part of soda are added dropwise at the same time so that the phenol is added, the temperature of the reaction mixture reaction mass is maintained neutral to weakly alkaline is allowed to rise to C., and 10 parts of a normal throughout. To the neutral mixture 7 parts of m0no- 35 solution of caustic soda are slowly introduced dropwise ethanolarnine are added, the temperature is raised to 70- in the course of 3 hours so that the reaction mixture is 75 C. in the course of 1-2 hours, the whole is stirred at maintained neutral to weakly alkaline throughout. 0.7 this temperature for 5 hours while the hydrochloric acid part of mono-ethanolamine is then added to the neutral formed is neutralized by the gradual addition of a solureaction mixture, the temperature is raised to 70 -75 C., tion of 5.3 parts of sodium carbonate in 50 parts of water. and stirring is continued for 6 hours at this temperature The whole is then allowed to cool, sodium chloride soluwhile the hydrochloric acid formed is neutralized by the tion is added, the precipitated condensation product is gradual addition of 0.5 part of sodium carbonate in 5 separated by filtration, washed with sodium chloride soluparts of water. The whole is then allowed to cool, sodium tion and the resulting disodium salt of 4:4'-bis-[2-phenylchloride is added, and the precipitated condensation thio-4 (fi-hydroxyethylamino)-l:3:5triazyl-(6) -amino]- product is separated by filtration, washed with sodium stilbene-2:2-disulfonic acid of the formula chloride solution and dried. The resulting disodium salt N N HOCHzCHrHN-C C-NH CH=CHONHC C-NHCHzCHzOH i it Q g i ll s's OsH 01H is dried. It is a pale yellow powder which is soluble of 4-[2-phenoxy-4-( fi-hydroxyethylamino)- 1:33:5-triazyl in water. Wool which has been treated with an aqueous (6) -amino]-4-[2-ethylamino-4-(ortho-anisidino) 123:5- solution of this product in the presence of an acid, for triazyl-(6)-amino]-stilbene-2:2'-disulfonic acid of the example, acetic acid, has a whiter appearance than wool formula EocmomNH-o C-NH OH=OH- NH-G C-NH ll r'r r r l 0 H SOIH CH:

C r NHCHzCH:

which has been treated without this addition. By using is a pale powder which dissolves in water to give a bluish instead of mono-ethanolamine, an equivalent quantity of fluorescence in ultraviolet light.

-morpholine,-or, instead of thiophenol an equivalent quan- By using instead of 0.95 part of phenol an equivalent tity of 2:5-dimethyl-thiophenol, or 2-mercapto-thiazoline quantity of a-naphthol or, instead of 4-amino-4-[2-ethylof the formula amino-4-(ortho-anisidino)-l :3 :5-t1'iazyl-(6)-amin0] stil- OHPN bene-2:2-disulfonic acid, an equivalent quantity of 4- amino 4'-[2 ethylamino-4-(orthochloranilino) 113:5-

triazyl-( 6)-amino]-stilbene-2:2'-disulfonic acid there are obtained products having similar properties, for example,

13 the disodium salt of 4-[2-(a-naphthoxy-4-(p-hydroxyethylamino)-l :3 :5-triazyl-( 6) -amino] -4- [2 ethylamino- 4 (orth-auisidino)-l:3:5-triazyl-(6)-amin0] stilbene- 2 2-disulfonic acid.

The 4-amino 4 [2-ethylamino-4-(ortho-anisidino)- 1:3:5-triazyl-(6) amino] stilbene-2z2' disulfonic acid used as starting material can be obtained in a manner analogous to that described in Example 4 for making 4- amino-4'-[2-methyl-amino-4 ([3 hydroxyethylamino)- 1:3 :5-triazyl-(6)-amino]-stilbene-2:2-disulfonic acid, by condensing 1 molecular proportion of 4-nitro-4-aminostilbene-2:2'-disulfonic acid with 1 molecular proportion of cyanuric chloride, 1 molecular proportion of ethylamine and 1 molecular proportion of ortho-anisidine and then reducing the resulting product.

Example 8 The disodium salt of 4-nitro-4-[2:4-dichloro-l:325- triaZyl- (6)-amino]-stilbene-2:2-disulfonic acid is prepared by the procedure described in Example 4 from 19 parts of cyanuric chloride and 47.6 parts of 4-nitro-4- aminostilbene-Z:2-disulfonic acid of 84 percent strength.

To the neutral reaction mixture free from starting material 9.5 parts of phenol are added, the temperature is raised to 40 C., the Whole is stirred at this temperature while 100 parts of a normal solution of caustic soda is run in in such manner that the reaction mixture is maintained neutral to weakly alkaline. After the addition of 18 parts of mono-ethanolamine the temperature is raised to 60-65 C., and the whole is stirred for 18 hours at that temperature. After cooling, sodium chloride solution is added to the reaction mixture, the precipitated condensation product is separated by filtration, washed with sodium chloride solution and reduced as described in Example 4.

The 4-arnino-4'-[2-phenoxy-4-(fi-hydroxyethylamino)- 1:3:5-triazyl (6) amino]-stilbene-2:2'-disulfonic acid washed free from mineral acid is stirred with 500 parts of Water and neutralized by the addition of sodium carbonate. The solution so obtained is added at 0-5 C. in the course of 10 minutes to a finely divided aqueous suspension of 18.5 parts of cyanuric chloride, and the reaction mass is then neutralized at 010 C. with a solution of 5.5 parts of sodium carbonate in 50 parts of water. As soon as the starting material has disappeared,

25 parts of diethanolamine are added, the temperature of the reaction mixture is raised to 35 C. and the whole is stirred for 4 hours at that temperature. After cooling, sodium chloride solution is added, the condensation product so precipitated is separated by filtration, washed with sodium chloride solution and dried. The resulting disodium salt of 4-[2-phenoxy-4-(,B-hydroxyethylamino)- 1:3:5-triazyl-(6)-aminol4-[2-chloro-4-(bis-;8 hydroxyethyl)-amino-1:3:5-triazyl (6) amino]-stilbene-2:2-disulfonic acid of the formula T4 is a pale yellow powder soluble in water.

A mixture of products having similar properties to those of the compound described above is obtained by condensing 1 molecular proportion of 4:4'-diaminostilbene-2:2-disu1fonic acid with 2 molecular proportions of cyanuric chloride, then reacting the condensation product with 1 molecular proportion of phenol and finally with 1 molecular proportion each of diethanolamine and ethanolamine.

Example 9 By the procedure described in Example 4 there is obtained 4-amino-4'- [2 4-di(ortho-chloranilino) -1 :3 5 -triazyl-(6)-amino]-stilbene-2:2'-disulfonic acid by condensing $5 of a molecular proportion of 4-nitro-4'-aminostilbene-2:2-disulfonic acid, A of a molecular proportion of cyanuric chloride and A of a molecular proportion of ortho-chloraniline and subsequently reducing the product. 7 parts of the acid so obtained are stirred with parts of water and neutralized by the addition of sodium carbonate. The solution so obtained is run at 05 C. in the course of 10 minutes into a finely divided aqueous suspension of 1.9 parts of cyanuric chloride, and a solution of 0.5 part of sodium carbonate in 5 parts of water is then slowly added to the reaction mass at Ol0 C. As soon as the starting material has disappeared, 0.5 part of monoethylamine is added, and the reaction temperature is raised to 35 C., and maintained thereat for 4 hours. The hydrochloric acid formed is neutralized by the addition of a solution of 0.5 part of sodium carbonate in 5 parts of water. There are then added 2.3 parts of the sodium salt of para-hydroxybenzene sulfonic acid, the reaction temperature is raised to 85 C., and the whole is stirred for 10 hours at this temperature while 10 parts of a normal solution of caustic soda are added dropwise so that the reaction mass is maintained neutral to weakly alkaline. After the addition of sodium chloride solution, the whole is allowed to cool, and the precipitated condensation product is separated by filtration, washed with sodium chloride solution and dried. The resulting trisodium salt of 4-[2-(parasulfophenoxy)-4-ethylamino -1:3:5 triazyl-(6)-amino]- 4-[2:4-di(ortho chloranilino)-1 :3 5-triazyl-(6)-amino]- stilbene-2:2'-disulfonic acid of the formula is a pale yellow powder which in aqueous solution exhibits a bluish fluorescence in ultraviolet light.

Example 10 8.7 parts of the disodium salt of 4-[2-chloro-4-(B- hydroxyethylamino) 1:3:5 triazyl-(6)-amino]-4-[2:4- di(bis-/3 hydroxyethyl)-amino-1:3:5-triazyl-(6)-aminolstilbene-2:2-disulfonic acid are stirred with parts of water at 40-50 C. 2 parts of Z-mercapto-benzthiazole are added. The reaction temperature is raised to 75 C.

CHzCHzOH & OHICHzOH chloride solution and dried. The resulting disodium salt of 4-[2-(2-mercapto-benzthiazolyl) 4 (fl-hydroxyethylamino)-l:3:5-triazyl-(6)-amino] 4' [2:4-di-(bis-{3-hydroxyethyl)-amino 1:3:5 triazyl-(6)-amino]-stilbene- 2:2-disulfonic acid of the formula HO GHzOHaNH-C is a yellow powder soluble in water.

By using, instead of Z-mercapto-benzthiazole an equivalent quantity of the sodium salt of thioglycollic acid there is obtained the trisodium salt of 4-[2-(thioglycollyl) 4 (B-hydroxyethylamino) 123:5 triazyl-(6)- amino] 4' [2:4-di-(bis-fl-hydroxyethyl)-amino 1:3:5- triazyl-(6)-an1ino]-stilbene-2:2-disulfonic acid which has similar properties.

A product with similar properties is also obtained by using instead of 4-[2-chloro-4-(B-hydroxyethylamino)- 1:3:5 triazyl (6) amino] 4' [2:4 di (bis )8- hydroxyethyl) amino 1:3:5 triazyl (6) amino]- stilbene-Z:2-disulfonic acid, 4-[2-chlor0-4(,B-hydroxyethylamino) 1:3:5 triazyl (6) amino] 4 [2 amino 4 (bis fi hydroxyethylamino 1:3:5 triazyl (6)- amino]-stilbene-2:2'-disulfonic acid, which can be prepared by reacting 1 molecular proportion of 4-nitro-4'- [2:4-dichloro-1:3:5-triazyl-(6)-amino]-stilbene-2:2 disulfonic acid with 1 molecular proportion each of ammonia and diethanolamine, reducing the nitro group to the amino group, condensing the reduction product with 1 molecular proportion of cyanuric chloride and reacting the condensation product with 1 molecular proportion of ethanolamine.

Furthermore, there are obtained products with similar properties by using as starting materials 4-[2-chloro-4- (B-hydroxyethylamino) 1:315 triazyl (6) amino]- 4 [2 morpholino 4 (bis ,8 hydroxyethylamino)- l:3:5-triazyl-(6)-amino]-stilbene-2:2-disulfonic acid, 4- [2 chloro 4 (ortho anisidino) 1:3:5 triazyl (6)- amino] 4' [2:4 di (bis ,8 hydroxyethy1amino)- l :3 :5 -triazyl-(6)-arnino]-stilbene-2:2'-disulfonic acid or 4 [2 chloro 4 (B hydroxyethylamino) 1:3:5 triazyl (6) amino] 4' [2 phenoxy 4 (bis 9 hydroxyethylamino) 1:3:5 triazyl (6) amino] stilbene-2 2'-disulfonic acid.

Example 11 Undyed cotton yarn is treated at a goods-to-liquor ratio of 1:30 for about hour at room temperature in a bath containing, per liter, 0.01 gram of the condensation product obtained as described in Example 1. After rinsing and drying the yarn so treated has a greater whiteness than the material not so treated.

Example 12 Undyed wool is treated at a goods-to-liquor ratio of 1:40 for /2 hour at 40-45 C. in a bath containing, per liter, 0.05 gram of the condensation product obtained as described in Example 2 and 1.25 grams of formic acid. After rinsing and drying, the wool so treated has a greater whiteness than the original material not so treated.

Example 13 The sodium salt of 2-heptadecyl-N-benzyl-benzimidazyl disulfonic acid is mixed with 0.05O.5 percent of its weight of the condensation product obtained as described in Example 3. Undyed textile goods, which have been washed in the usual manner with the resulting mixture, exhibit a brighter appearance than textile goods which have been washed with the aforesaid sodium salt alone.

Example 14 Cotton is washed at the boil at a goods-to-liquor ratio /N\ CHzCHzOH NEH.) PK

N Di CHgCHaOH CHzCHaOH of 1:40 in a bath containing, per liter, 10 grams of a washing preparation having the following composition:

33.3% of soap,

11.0% of calcined sodium carbonate,

14.0% of sodium pyrophosphate,

7.0% of sodium perborate,

3.0% of magnesium silicate,

0.1% of the product obtainable as described in Example 7, 31.6% of water.

The cotton is then rinsed and dried. It has a whiter appearance than cotton which has been washed with a washing preparation of the same composition except that it does not contain the addition of the product obtained as described in Example 7.

What is claimed is:

1. An optical bleaching preparation which contains at least one washing agent and at least one optical bleaching agent consisting essentially of a water-soluble salt of a colorless to substantially colorless derivative of 4:4- diamino-stilbene-Z:2-disulfonic acid of the formula N N C-HNOOH=CHONH-C \OY l1 I I l 1 1 ll SOaH SOaH C C l l in which W represents a member selected from the group consisting of aromatic radicals containing at most two carbocyclic rings and being bound to the carbon atom of the triazine ring by an -O-bridge, lower alkyl radicals, lower hydroxyalkyl radicals, aromatic radicals containing one carbocyclic ring and heterocyclic radicals containing at most two rings and being bound to the carbon atom of the triazine ring by an --S-bridge, X and Y each represents a radical of nitrogenous base, which base contains at least one hydrogen atom attached to the nitrogen atom and is selected from the group consisting of ammonia, lower alkylamines, lower hydroxyalkyl)-amines, lower N':N'-dialkyl-alkylene diamines, aromatic amines containing at most two carbocyclic rings and heterocyclic amines containing one ring of which the amine nitrogen atom is a ring member, the radicals of said nitrogenous bases being attached by the nitrogen atom to the triazine ring, and Z represents a member of the group consisting of a chlorine atom and of radicals of the kind represented by W, X and Y, all substituents being free from groups imparting dyestutf characteristics to the molecule.

2. A process for enhancing the brightness of organic fibrous material which comprises impregnating the material with an aqueous solution of an optical bleaching agent consisting essentially of a water-soluble salt of a colorless to substantially colorless derivative of ,4z51f-di- 'amino-stilbene 2:2-disulfonicacid of' the formula' scan sents a radical of a nitrogenous base, which base contains I at least one hydrogen atom attached to the nitrogen atom and is selected from the group consisting of ammonia, lower alkylamines, lower (hydroxyalkyl)-amines, lower N:N'-dialkyl-alkylene-diamines, aromatic amines conamines containing one ring of which the amine nitrogen atom is a ring member, the radicals of said nitrogenous bases being attached by the nitrogen atom to the triazine ring, andZ represents a member of the group consisting of a chlorine atom and of radicals of the kind represented 33 by W, X and Y, all substituents being free from groups imparting dyestufi characteristics to the molecule.

3. A process for enhancing the brightness of organic fibrous material which comprises impregnating the mateagent consisting essentially of a water-soluble salt of a colorless to substantially colorless derivative of 4: 4-diamino stilbene-2:2-disulfonic acid of the formula N SOsH free from group imparting dyestuff characteristics to the molecule, and subsequently drying the impregnated material.

4. A process for enhancing the brightness of organic fibrous material which comprises impregnating the material with an aqueous solution of an optical bleaching agent consisting essentially of a Water-soluble salt of a colorless to substantially colorless derivative of 4:4-diamino-stilbene-Z:2'-disulfonic acid of the formula N \C N s osn N SOaH taining at most two carbocyclic rings and heterocyclic assess? in which and Z each represent a radical of a nitrogousb as e,fwhich base contains 'atleast one hydrogen atom attached to'fthenitrogen atom and is selected from the group consisting of ammonia, lower alkylarnines, lower (hydroxyalkyl) -amines, .low er .N' N-dialkyl-alkyl- :enediamin'es, aromatic amines containing atmost two carbocyclic rings and heterocyclic airlines containing one "ring of which the amine nitrogen atom is a ring member, the radicals of said nitrogenous bases being attached by the nitrogen atom to the triazinering, and R represents a radical of the benzene series, all substituents being free from groups imparting -dyestuff characteristics to the molecule, and subsequently drying the impregnated material.

5. A process for enhancing the ,brightness of organic fibrous material which comprises impregnating the 'rnaterial with an aqueous solution of'an optical bleaching agent consisting essentially of a water-soluble salt of a colorless to substantially colorless derivative of 4:4'-diamino -stilbene-2:2' disulfonic acid of the formula 1 1 V \O S Q SOsH in which X and Y eachrepresents a radical of a nitrogenous base, whichbase contains at least one hydrogen atomatta-ched to the nitrogen atom and is selectedfrom the group consisting of ammonia, lower aljkylamine's,

v r lower (hydroxyalkyl)-amines,'lower N';N-dialkyl-alkylrial with an' aqueous solution of an optical bleach ng y 0 ene diamines, aromatic amines containing at most two carbocyclic rings and heterocyclic amines containing one ring of which the amine nitrogen atom is a ring'member, the radicals of said nitrogenous bases being attached by the nitrogen atom tothe tria zine ring and R represents a member selected from the group consisting oflower alkyl radicals, lower ,hydroxyallgyl radicals, aromatic radicals containing one carbocyclic ring and heterocyclic radicals containing at most two rings, all substituents being free from groups imparting dyestufi characteristics to the molecule, and subsequently drying the impregnated material. t

6. A process for enhancing the brightness of organic fibrous material which comprises impregnating the material with an aqueous solution of an optical bleaching agent consisting essentially of a water-soluble salt of a colorless to substantially colorless derivative of 4:4-diamine-stilbene-Z:2'-disulfonic acid of the formula K A0,]; scan s as l in which X, Y and Z each represents a radical of a nitrogenous base, which base contains at least one hydrogen atom attached to the nitrogen atom and is selected from the group consisting of ammonia, lower alkylamines, lower (hydroxyalkyl)-amines, lower N:N-dialkyl-alkylene diamines, aromatic amines containing at most two carbocyclic rings and heterocyclic amines containing one ring of which the amine nitrogen atom is a ring member, the radicals of said nitrogenous bases being attached by the nitrogen atom to the triazine ring and R represents a member selected from the group consisting of lower alkyl radicals, lower hydroxyallsyl radicals, aromatic radicals containing one carbocyclic ring and heterocyclic bis [2 -phenoxy 4 ethylamino 1:3:5 triazyl (6)- amino]-stilbene-2:2'-disulfonic acid and subsequently drying the impregnated material.

8. A process for enhancing the brightness of organic fibrous material which comprises impregnating the material with an aqueous solution of an optical bleaching agent consisting essentially of an alkali metal salt of 4:4-

bis [2 phenoxy 4 8 hydroxyethylamino) 113:5- triazyl (6) amino] stilbene 2:2 disulfonic acid and subsequentlydrying the impregnated material.

9. A process for enhancing the brightness of organic fibrous material which comprises impregnating the material with an aqueous solution of an optical bleaching agent consisting essentially of an alkali metal salt of 4-[2- phenoxy 4 ([3 hydroxyethylamino) 1:3:5 triazyl- (6) amino] 4 [2 ethylamino 4 (ortho anisidino) 1:3:5 triazyl (6) amino] stilbene 2:2- disulfonic acid and subsequently drying the impregnated material.

10. A process for enhancing the brightness of organic fibrous material which comprises impregnating the material with an aqueous solution of an optical bleaching agent consisting essentially of an alkali metal salt of 4:4- bis [2 phenylthio 4 8 hydroxyethylamino)- 1:3:5 triazyl (6) amino] stilbene 2:2 disulfonic acid and subsequently drying the impregnated material.

11. A processfor enhancing the brightness of organic fibrous material which comprises impregnating the material with an aqueous solution of an optical bleaching agent consisting essentially of an alkali metal salt of 4-[2- (2 mercapto benzthiazolyl) 4 ()3 hydroxyethylamino) 1:3:5 triazyl (6) amino] 4 [2:4 di- (bis ,3 hydroxyethylamino) 1:3:5 triazyl (6)- amino] stilbene 2:2 disulfonic acid and subsequently drying the impregnated material.

20 12. Fluorescent agents which in the form of the free acid have the formula 13. An optical bleaching preparation which contains at least one washing agent and an optical bleaching agent consisting essentially of an alkali metal salt of 4:4 bis- [2 phenoxy 4 ethylamino 1:3:5 triazyl (6)- amino] -stilbene-2 2-disulfonic acid.

14. An optical bleaching preparation which contains at least one washing agent and an optical bleaching agent consisting essentially of an alkali metal salt 'of 4:4-bis- [2 phenoxy 4 (5 hydroxyethylamino) 1:3:5- triazyl- (6 -amino] -stilbene-2 2-disulfonic acid.

15. An optical bleaching preparation which contains at least one washing agent and an optical bleaching agent consisting essentially of an alkali metal salt of 4-[2-phenoxy 4 3 hydroxyethylamino) 1:3:5 triazyl (6)- amino] 4 [2 ethylamino 4 (ortho anisidino)- l :3 :5-triazyl-(6)-amino] -stilbene-2:2-disulfonic acid.

References Cited in the file of this patent UNITED STATES PATENTS 564,835 Newman July 28, 1896 2,171,427 Eggert Aug. 29, 1939 2,221,361 Schmid NOV. 12, 1940 2,368,844 Keller Feb. 6, 1945 2,376,743 Wendt May 22, 1945 2,473,475 Keller June 14, 1949 2,539,766 Zweidler Jan. 30, 1951 FOREIGN PATENTS 596,405 Great Britain Jan. 2, 1948 UNITED STATES PATENT OFFICE QERTIFEATE @F QURRECTION Patent No, 2;,846,39'7 August 5, 1958 Franz Ackermann It is herebfl certified that error appears in the-printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 40, for "of" read or line 43, for "of", second occurrence, read M or line 55, for "chloride of" read chloride or same line, for "bromine" read um bromide line 57 for "salts" read salt line 62, for "bromine" read me bromide column '7, line 15, for "ofg" read me of column 10, line 19, for "in neutralized" read is neutralized column 16, line 59 for "of nitrogenous read M of a nitro genous line 62, for "hydroxyalkyl) -=-amines" read me (hydroXyalkyl)-=amines Signed and sealed this 14th day April 1959 (SEAL) fittest:

KARL H. AXLINE ROBERT C. WATSON Attesting Oflicer Commissioner of Patents 

2. A PROCESS FOR ENHANCING THE BRIGHTNESS OF ORGANIC FIBROUS MATERIAL WHICH COMPRISES IMPREGNATING THE MATERIAL WITH AN AQUEOUS SOLUTION OF AN OPTICAL BLEACHING AGENT CONSISTING ESSENTIALLY OF A WATER-SOLUBLE SALT OF A COLORLESS TO SUBSTANTIALLY COLORLESS DERIVATIVE OF 4:4''-DIAMINO-STILBENE-2:2''-DISULFONIC ACID OF THE FORMULA
 12. FLUORESCENT AGENTS WHICH IN THE FORM OF THE FREE ACID HAVE THE FORMULA 